Synfacts 2008(3): 0300-0300  
DOI: 10.1055/s-2008-1042732
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

ortho-Selective Cross-Coupling of Dichlorobenzenes with Grignard Reagents

Contributor(s):Paul Knochel, Andrei Gavryushin
S. Ishikawa, K. Manabe*
RIKEN, Wako, Japan
Highly Ortho-Selective Cross-Coupling of Dichlorobenzene Derivatives with Grignard Reagents
Org. Lett.  2007,  9:  5593-5595  
Further Information

Publication History

Publication Date:
21 February 2008 (online)


Significance

The problem of the regioselectivity in cross-coupling reactions of functionalized di­haloarenes is important from the practical point of view. In this publication, the authors demonstrated highly ortho-selective coupling reactions of dichlorinated phenols, anilines and their derivatives, bearing an anionic coordinating group. Aryl, hetaryl, and alkenylmagnesium halides are suitable coupling partners. Using a specially designed ligand 1, o-chlorine can be coupled preferentially in the presence of a bromine atom in another position.

Comment

Many examples of regioselective cross-coupling of dihaloheteroarenes are known (see review below). Ishikawa and Manabe also recently reported the ortho-selective coupling of dibromophenols and dibromoanilines, using the terphenyl ligand 1 (see scheme; Chem. Lett. 2007, 36, 1304). A similar reaction with arylboronic acids as nucleophiles failed to give any significant regio­selectivity.

Review

S. Schröter, C. Stock, T. Bach Tetrahedron 2005, 61, 2245.